N-substituted arylcyclo butenyl-unsaturated cyclic imides

ABSTRACT

The invention is a compound which comprises an unsaturated cyclic imide moiety and an aryl cyclobutene moiety, wherein the cyclobutene moiety is fused to the aryl radical, and wherein the imide nitrogen is connected to the aryl radical by a direct bond or a bridging member. Another aspect of this invention is a polyimide polymeric composition which results from the polymerization of the above-described compounds.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 893,125 filed Aug. 4, 1986,now U.S. Pat. No. 4,826,997 which is a continuation-in-part of aco-pending application Ser. No. 644,849 filed Aug. 27, 1984 nowabandoned. (incorporated herein by reference).

BACKGROUND OF THE INVENTION

This invention relates to N-substituted arylcyclobuteno-unsaturatedcyclic imides, and to novel polyimides prepared from such compounds.

In recent years the search for high performance materials, especiallyhigh temperature-resistant polymers, has gained momentum. In order for amaterial to have stability at high temperatures, it must fulfill severalrequirements including a high melting or softening temperature, a highmodulus or rigidity, a resistance to solvent and chemical degradation,and toughness. The intrinsic thermal and oxidative stability of aromaticstructures has long been recognized, and a variety of polymers have beenmade in which benzene rings are linked together by various connectinggroups. Among the more stable aromatic polymers that fulfill therequirements of high temperature resistance are the polybenzimidazoles,the polybenzoxazoles and the polyimides. Of these polymers, thepolyimides have had the most interest.

The major difficulty encountered in the commercial development of thesematerials is that they are usually obtained in the form of a powderwhich cannot be readily fabricated into useful objects.

The polyimides prepared from aliphatic diamines and aromatic carboxylicacids are generally soluble and thermoplastic. Aliphatic polyimides havebeen prepared from bis(dienophiles) and a diene such as cyclopentadiene.Such reactions often involve gas evolution.

Aromatic polyimides, such as polypyromellitimides, have a spectrum ofsuperior properties. Those polyimides may be prepared by the reaction ofan aromatic dianhydride with an aromatic diamine to give a solublepolyamic acid, which on cyclodehydration gives the insoluble desiredproduct.

High performance plastics reduce the weight of mechanical components,and not just by virtue of their densities. Their high performanceproperties allow greater design stresses, and often elements can bedownsized accordingly. In recent years, aromatic polyimides have becomewidely accepted as premium, high performance engineering plastics. Theseresins are well-known for having excellent properties at elevatedtemperatures (i.e., chemical resistance) but are also costly.Historically, polyimide resins are difficult to fabricate into objectsother than fibers and films. The most common methods of manufacturingparts having the highest strength and temperature properties are hotcompression-molding, machining from hot-compression molded or extrudedrod, and direct forming (a process similar to the powder-metallurgyprocesses). Given the synthetic and fabrication difficulties, a newroute to polyimides is desirable.

A further problem with the preparation of certain polyimides is the needfor the use of catalysts, initiators or curing agents. The presence ofsuch compounds often results in the preparation of impure polymericcompositions. Further, the presence of such compounds often results inundesirable properties in such polymeric compositions. What are neededare monomers which prepare polyimides wherein the polymers can be easilyprocessed, for example, fabricated into useful objects. What are furtherneeded are monomers which can be polymerized in a manner such that nogas is evolved. What are further needed are monomers which can bepolymerized without the need for catalysts, curing agents or initiators.

SUMMARY OF THE INVENTION

The invention is a compound which comprises an unsaturated cyclic imidemoiety and an aryl cyclobutene moiety, wherein the cyclobutene moiety isfused to the aryl radical, and wherein the imide nitrogen is connectedto the aryl radical by a bridging member or a direct bond.

Another aspect of this invention is a polyimide polymeric compositionwhich results from the polymerization of one or more of theabove-described compounds.

The novel compounds of this invention are easily processable into usefularticles. The polymerization of such compounds does not result in theevolution of gaseous or volatile by-products which can create problemsin the eventual product prepared. Furthermore, in order to prepare thepolymers of these monomers, there is no need for catalysts, initiatorsor curing agents.

DETAILED DESCRIPTION OF THE INVENTION

In general, the compounds of this invention comprise unsaturated cyclicimides which are N-substituted with arylcyclobutene moieties. In sucharylcyclobutene moieties the cyclobutene ring is fused to the aromaticradical. The nitrogen atom of the cyclic imide is connected to the arylradical of the arylcyclobutene moiety by a bridging member or a directbond. The cyclic imide can be substituted with hydrocarbyl,hydrocarbyloxy or hydrocarbylthio substituents. The aryl radical on thearylcyclobutene moiety can be substituted with electron-withdrawinggroups, electron-donating groups, hydrocarbyl groups, hydrocarbyloxygroups or hydrocarbylthio groups. The cyclobutene ring may besubstituted with electron-withdrawing groups or electron donatinggroups.

The cyclic imide can be any cyclic imide moiety which contains olefinicunsaturation, and which may be substituted in the manner describedhereinbefore. It is preferable that the olefinic unsaturation beadjacent to one of the carbonyl moieties of the imide functionality. Inone preferred embodiment, the cyclic imide is a 5-membered heterocycle,in particular, a maleimide. Preferably, the substituents which may be onthe carbon atoms of the imide ring are C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₁₋₂₀alkylthio, C₆₋₂₀ aryl, C₆₋₂₀ aryloxy, C₆₋₂₀ arylthio, C₇₋₂₀ alkaryl,C₇₋₂₀ alkaryloxy, C₇₋₂₀ alkarylthio, C₇₋₂₀ aralkyl, C₇₋₂₀ aralkoxy orC₇₋₂₀ aralkylthio. More preferred substituents include C₁₋₂₀ alkyl, withC₁₋₃ alkyl being most preferred.

The arylcyclobutene moiety can be any aromatic radical which has acyclobutene ring fused to one of the aromatic rings. The term "aryl"refers herein to any aromatic radical. Aromatic as used herein refers tocarbocyclic or heterocyclic rings in which 4n+2 delocalized π electionsare contained in an orbital ring. This property is also known asresonance stabilization or delocalization. Preferred carbocyclicaromatic radicals include benzene, naphthalene, phenanthrene,anthracene, a biaryl radical, or two or more aromatic radicals bridgedby alkylene or cycloalkylene moieties. More preferred carbocyclicaromatic radicals include benzene, naphthalene, biphenyl, binaphthyl ora diphenylalkylene or a diphenylcycloalkylene compound. The mostpreferred carbocyclic aromatic radical is benzene. Examples of preferredheterocyclic aromatic compounds included pyrrole, furan, thiophene,imidazole, oxazole, thiazole, pyrazole, pyridine, and pyrimidine. Morepreferred heterocyclic aromatic compounds are pyridine, furan, andthiophene, with pyridine being most preferred. The carbocyclic aromaticrings are preferred over the heterocyclic aromatic rings.

The aryl radical can be substituted with electron-withdrawing groups,electron-donating groups, hydrocarbyloxy groups, hydrocarbyl groups orhydrocarbylthio groups. Electron-withdrawing groups refer herein tocyano, carboxylate, hydrocarbylcarbonyloxy, nitro, halo,hydrocarbylsulfinyl or hydrocarbylsulfonyl groups. Electron-donatinggroups refer herein to amino groups, hydroxy groups or alkyl groups.Preferred substituents on the aryl radical include C₁₋₂₀ alkyl, C₁₋₂₀alkoxy, C₁₋₂₀ alkylthio, C₆₋₂₀ aryl, C₆₋₂₀ aryloxy, C₆₋₂₀ arylthio,C₇₋₂₀ alkaryl, C₇₋₂₀ alkaryloxy, C₇₋₂₀ alkarylthio, C₇₋₂₀ aralkyl, C₇₋₂₀aralkoxy, C₇₋₂₀ aralkylthio, cyano, carboxylate, hydrocarbylcarbonyloxy,nitro, halo, hydrocarbylsulfinyl, amino or hydrocarbylsulfonyl. Morepreferred substituents on the aryl radical include C₁₋₂₀ alkyl, halo,nitro or cyano. The most preferred substituents on the aryl moietyinclude C₁₋₃ alkyl, halo, nitro or cyano.

The cyclobutene ring may be substituted with electron-withdrawing groupsor electron donating groups, wherein electron-withdrawing groups andelectron-donating groups are described hereinbefore. Preferredsubstituents on the cyclobutene ring are cyano, carboxylate,hydrocarbylcarbonyloxy, nitro, halo, hydrocarbylsulfonyl orhydrocarbylsulfinyl. More preferred substituents include halo, nitro orcyano groups; with cyano groups being most preferred.

The bridging member can be a divalent organic radical which is bonded tothe nitrogen of the cyclic imide and the aryl radical of thearylcyclobutene moiety. The divalent organic radical useful as abridging member is any divalent organic radical which is capable ofbeing bonded to both the nitrogen of a cyclic imide and an aryl radical.The divalent organic radical is preferably a hydrocarbylene,hydrocarbyleneamido, hydrocarbylenecarbonyloxy, hydrocarbyleneoxy,hydrocarbylenethio, hydrocarbylenesulfinyl or hydrocarbylenesulfonylradical. More preferred divalent organic radicals are alkylene, arylene,alkylene-bridged polyarylene, cycloalkylene-bridged polyarylene,alkyleneamido, aryleneamido, alkylene-bridged polyaryleneamido,cycloalkylene-bridged polyaryleneamido, alkylenecarbonyloxy,arylenecarbonyloxy, alkylene-bridged polyarylenecarbonyloxy,cycloalkylene-bridged polyarylenecarbonyloxy, alkyleneoxy, aryleneoxy,alkylene-bridged polyaryleneoxy, cycloalkylene-bridged polyaryleneoxy,alkylenethio, arylenethio, alkylene-bridged polyarylenethio,cycloalkylene-bridged polyarylenethio, alkylenesulfinyl,arylenesulfinyl, alkylenebridged polyarylenesulfinyl,cycloalkylene-bridged polyarylenesulfinyl, alkylenesulfonyl,arylenesulfonyl, alkylene-bridged polyarylenesulfonyl orcycloalkylene-bridged polyarylenesulfonyl. Even more preferred divalentorganic radicals include alkylene, arylene, alkylenecarbonyloxy,arylenecarbonyloxy, alkyleneamido, aryleneamido, alkyleneoxy,aryleneoxy, alkylenethio or arylenethio. Most preferred divalent organicradicals include alkylene and arylene radicals.

Preferably, the aryl moiety and cyclic imide are connected by a directbond or a bridging member which comprises an alkylene, arylene,alkylene-bridged polyarylene or cycloalkylene-bridged polyarylene; andmore preferably a direct bond or a bridging member which comprises analkylene or arylene moiety. Most preferably the cyclic imide nitrogenand the aryl radical are connected by a direct bond.

Preferred N-substituted arylcyclobutenyl cyclic imides correspond to theformula ##STR1## wherein

Ar is an aromatic radical;

R¹ is separately in each occurrence a hydrocarbyl, hydrocarbyloxy,hydrocarbylthio, electron-donating or electron-withdrawing group;

R² is separately in each occurrence hydrogen or an electron-withdrawinggroup;

X is an alkenylene moiety which can be substituted with one or morehydrocarbyl, hydrocarbyloxy or hydrocarbylthio groups;

Y is a direct bond or divalent organic moiety; and

a is an integer of between about 0 and 3.

More preferred N-substituted arylcyclobutenyl-unsaturated cyclic imidesinclude those which correspond to the formula ##STR2## wherein

Ar is an aromatic radical;

R¹ is separately in each occurrence a hydrocarbyl, hydrocarbyloxy,hydrocarbylthio, an electron-donating or electron-withdrawing group;

R² is separately in each occurrence hydrogen or an electron-withdrawinggroup;

R³ is separately in each occurrence hydrogen, a hydrocarbyl,hydrocarbyloxy or hydrocarbylthio group;

Y is a direct bond or a divalent organic radical; and

a is an integer of between about 0 and 3.

In an even more preferred embodiment, the N-substitutedarylcyclobutenyl-unsaturated cyclic imide corresponds to the formula##STR3## wherein

R¹ is separately in each occurrence a hydrocarbyl, hydrocarbylthio,hydrocarbyloxy, electron-withdrawing or electron-donating group;

R² is separately in each occurrence hydrogen or an electron-withdrawinggroup;

R³ is separately in each occurrence hydrogen, hydrocarbyl,hydrocarbyloxy or hydrocarbylthio;

Y is a direct bond or a divalent organic radical; and

b is an integer of between 0 and 3, inclusive.

In the above formulas, R¹ is preferably C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₁₋₂₀alkylthio, C₆₋₂₀ aryl, C₆₋₂₀ aryloxy, C₆₋₂₀ arylthio, C₇₋₂₀ alkaryl,C₇₋₂₀ alkaryloxy, C₇₋₂₀ alkarylthio, C₇₋₂₀ aralkyl, C₇₋₂₀ aralkoxy,C₇₋₂₀ aralkylthio, cyano, carboxylate, hydrocarbylcarbonyloxy, nitro,halo, hydrocarbylsulfinyl, hydrocarbylsulfonyl or amino. R¹ is morepreferably C₁₋₂₀ alkyl, halo, nitro or cyano. Most preferably R¹ is C₁₋₃alkyl, halo, nitro or cyano.

R² is preferably hydrogen, cyano, carboxylate, hydrocarbylcarbonyloxy,nitro, halo, hydrocarbylsulfonyl hydrocarbylsulfinyl, alkyl, amido,hydrocarbyloxy. R² is more preferably hydrogen, halo, nitro or cyano. R²is even more preferably hydrogen or cyano and most preferably hydrogen.

R³ is preferably hydrogen, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₁₋₂₀ alkylthio,C₆₋₂₀ aryl, C₆₋₂₀ aryloxy, C₆₋₂₀ arylthio, C₇₋₂₀ alkaryl, C₇₋₂₀alkaryloxy, C₇₋₂₀ alkarylthio, C₇₋₂₀ aralkyl, C₇₋₂₀ aralkoxy or C₇₋₂₀aralkylthio. R³ is more preferably hydrogen or C₁₋₂₀ alkyl. R³ is evenmore preferably hydrogen or C₁₋₃ alkyl and most preferably hydrogen.

In the above formulas, Y is preferably a direct bond, a hydrocarbylene,hydrocarbyleneamido, hydrocarbylenecarbonyloxy, hydrocarbyleneoxy,hydrocarbyleneamino, hydrocarbylenecarbonyl, hydrocarbylenethio,hydrocarbylenepolythio, hydrocarbylenesulfinyl orhydrocarbylenesulfonyl. Y is more preferably a direct bond, alkylene,arylene, alkylene-bridged polyarylene, cycloalkylene-bridgedpolyarylene, alkyleneamido, aryleneamido, alkylenecarbonyloxy,arylenecarbonyloxy, arylenecarbonyl, alkylenecarbonyl, aryleneoxy,alkyleneoxy, aryleneamino, alkyleneamino, alkylenethio,alkylenepolythio, arylenethio, arylenepolythio, arylenesulfinyl,alkylenesulfinyl, arylenesulfonyl or alkylenesulfonyl. Y is mostpreferably a direct bond, alkylene or arylene.

In the formulas described hereinbefore, Ar is preferably a benzene,naphthalene, phenanthrene, anthracene or biaryl radical, or two or morearomatic radicals bridged by alkylene moieties. Ar is more preferablybenzene, naphthalene, biphenyl, binaphthyl or a diphenylalkylene. Ar ismore preferably a benzene radical.

Hydrocarbyl means herein an organic radical containing carbon andhydrogen atoms. The term hydrocarbyl includes the following organicradicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,aliphatic and cycloaliphatic aralkyl and alkaryl. Aliphatic refersherein to straight- and branched-, and saturated and unsaturated,hydrocarbon chains, that is, alkyl, alkenyl or alkynyl. Cycloaliphaticrefers herein to saturated and unsaturated cyclic hydrocarbons, that is,cycloalkenyl and cycloalkyl. The term aryl refers herein to biaryl,biphenylyl, phenyl, naphthyl, phenanthranyl, anthranyl and two arylgroups bridged by an alkylene group. Alkaryl refers herein to an alkyl-,alkenyl- or alkynyl-substituted aryl substituent wherein aryl is asdefined hereinbefore. Aralkyl means herein an alkyl, alkenyl or alkynylgroup substituted with an aryl group, wherein aryl is as definedhereinbefore. C₁₋₂₀ alkyl includes straight- and branched-chain methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl and eicosyl groups. C₁₋₅ alkyl includesmethyl, ethyl, propyl, butyl and pentyl.

Cycloalkyl refers to alkyl groups containing one, two, three or morecyclic rings. Cycloalkenyl refers to mono-, di- and polycyclic groupscontaining one or more double bonds. Cycloalkenyl also refers tocycloalkenyl groups wherein two or more double bonds are present.

Hydrocarbylene herein refers to a divalent hydrocarbon radical and isanalogous to the hydrocarbyl radicals described hereinbefore with thesingle difference that the hydrocarbylene radical is divalent.

Hydrocarbyleneamido refers herein to a divalent radical wherein ahydrocarbylene radical is bonded to an amido group, and corresponds tothe formula ##STR4## wherein R⁴ is a hydrocarbylene radical and R⁵ ishydrogen or a hydrocarbyl radical.

Hydrocarbyleneoxy refers herein to a divalent radical in which ahydrocarbylene radical is bonded to a divalent oxygen atom andcorresponds to the formula --R⁴ --O-- wherein R⁴ is as definedhereinbefore.

Hydrocarbylenecarbonyloxy refers to a hydrocarbylene moiety which isbonded to a carbonyl moiety which is further bonded to a divalent oxygenatom and corresponds to the formula ##STR5## wherein R⁴ is as definedhereinbefore.

Hydrocarbylenethio refers herein to a radical in which a hydrocarbyleneradical is further bonded to one or more sulfur moieties and correspondsto the formula --R⁴ --(S)-- wherein R⁴ is as hereinbefore defined, andwherein p is between 1 and 3.

Hydrocarbyleneamino refers herein to a hydrocarbylene radical bonded toan amino moiety and generally corresponds to the formula ##STR6##wherein R⁴ and R⁵ are as defined hereinbefore.

Hydrocarbylenesulfinyl refers herein to a hydrocarbylene moiety bondedto a sulfinyl moiety and generally corresponds to the formula ##STR7##wherein R⁴ is as hereinbefore defined.

Hydrocarbylenesulfonyl generally corresponds to a radical in which ahydrocarbylene radical is bonded to a sulfonyl radical and correspondsto the formula ##STR8## wherein R⁴ is as hereinbefore defined.

Wherein the bridging member is a hydrocarbyleneamido, hydrocarbyleneoxy,hydrocarbyleneamino, hydrocarbylenethio, hydrocarbylenecarbonyloxymoiety, the amido, amino, oxy, thio, sulfinyl or sulfonyl moiety ispreferably bonded to the aryl portion of the arylcyclobutene.

Examples of preferred N-substituted benzocyclobutenyl maleimides includeN-benzocyclobutenyl maleimide, N-benzocyclobutenylmethyl maleimide,N-benzocyclobutenylethyl maleimide, N-benzocyclobutenylpropyl maleimide,N-benzocyclobutenylbutyl maleimide, N-benzocyclobutenylpentyl maleimide,N-benzocyclobutenylhexyl maleimide, N-benzocyclobutenylphenyl maleimide,N-benzocyclobutenylbiphenyl maleimide, N-benzocyclobutenylamidomethylmaleimide, N-benzocyclobutenylamidoethyl maleimide,N-benzocyclobutenylamidopropyl maleimide, N-benzocyclobutenylamidobutylmaleimide, N-benzocyclobutenylamidopentyl maleimide,N-benzocyclobutenylamidohexyl maleimide, N-benzocyclobutenylamidophenylmaleimide, N-benzocyclobutenylamidobiphenyl maleimide,N-benzocyclobutenyloxycarbonylmethyl maleimide,N-benzocyclobutenyloxycarbonylethyl maleimide,N-benzocyclobutenyloxycarbonylpropyl maleimide,N-benzocyclobutenyloxycarbonylbutyl maleimide,N-benzocyclobutenyloxycarbonylpentyl maleimide,N-benzocyclobutenyloxycarbonylhexyl maleimide,N-benzocyclobutenyloxycarbonylphenyl maleimide,N-benzocyclobutenyloxycarbonylbiphenyl maleimide,N-benzocyclobutenylthiomethyl maleimide, N-benzocyclobutenylthioethylmaleimide, N-benzocyclobutenylthiopropyl maleimide,N-benzocyclobutenylthiobutyl maleimide, N-benzocyclobutenylthiopentylmaleimide, N-benzocyclobutenylthiohexyl maleimide,N-benzocyclobutenylthiophenyl maleimide, N-benzocyclobutenylthiobiphenylmaleimide, N-benzocyclobutenyloxymethyl maleimide,N-benzocyclobutenyloxyethyl maleimide, N-benzocyclobutenyloxypropylmaleimide, N-benzocyclobutenyloxybutyl maleimide,N-benzocyclobutenyloxypentyl maleimide, N-benzocyclobutenyloxyhexylmaleimide, N-benzocyclobutenyloxyphenyl maleimide,N-benzocyclobutenyloxybiphenyl maleimide.

The arylcyclobutene moieties can be prepared by several synthesisschemes.

In one synthesis scheme, an alkyl-substituted aromatic compound which isfurther substituted with an aryl deactivating substituent ischloroalkylated in a position ortho to the alkyl group. In the preferredembodiment wherein the aromatic compound is benzene, the startingmaterial corresponds to the following formula ##STR9## wherein R¹ and R²are defined hereinbefore; R⁹ is any aryl deactivating substituent; and cis an integer of 0, 1, 2, or 3. The alkyl N-substituted aromaticcompound is chloroalkylated by contacting the alkyl aromatic compoundwith a chloroalkylating agent and thionyl chloride in the presence of aniron chloride catalyst so as to result in a product which contains achloroalkyl group ortho to the alkyl substituent. In the embodimentwherein the aromatic compound is a benzene ring, the product correspondsto the formula ##STR10## wherein R⁹ is a hydrocarbyloxycarbonyl,carboxamide, hydrocarbylcarbonyl, carboxylate, halocarbonyl, nitrile,nitro, sulfone or sulfoxide group. R⁹ is more preferably a halo orhydrocarbyloxycarbonyl group, with hydrocarbyloxycarbonyl being the mostpreferred group. Preferably c is 0 or 1, most preferably 0.

In this process the chloroalkylating agent is preferably chloromethylmethyl ether, although other agents such as bis(chloromethyl) ethercould be used. At least a 2:1 molar excess of the chloroalkylating agentto the alkyl-substituted aromatic compound is needed. It is preferableto use between about a 6:1 and 3:1 ratio of chloroalkylating agent toalkyl aromatic compound. The catalyst is ferric chloride (FeCl₃) whilethe cocatalyst is thionyl chloride. The catalyst can be present inbetween about 0.1 and 1.0 mole per mole of alkyl aromatic. Morepreferably between about 0.2 and 0.4 mole of catalyst are present foreach mole of alkyl aromatic compound. Preferably between about 0.1 and1.0 mole of thionyl chloride per mole of alkyl aromatic is used, morepreferably between about 0.2 and 0.4 mole per mole of alkyl aromatic.

This process can be performed at a temperature of between about 40° C.and 80° C., preferably about 40° C. and 60° C. Below about 40° C., thereaction rate is low. The boiling point of some of the components of thereaction mixture starts at about 80° C.

This process can be done by contacting the alkyl aromatic compound withthe chloromethylating agent, catalyst and cocatalyst in a suitablesolvent. Suitable solvents include chlorinated hydrocarbon solvents.Thereafter the reaction mixture is heated to the appropriatetemperature.

The product can be recovered by quenching the reaction mixture withalcohols or water to inactivate the chloroalkylating agents remaining,stripping off the volatiles and washing out the catalyst with water. Theproduct thereafter is recovered by distillation.

The ortho chloroalkylated alkyl aromatic compounds can be converted toaromatic compounds with cyclobutene rings fused thereto, by pyrolysis.This is achieved by contacting the ortho chloroalkylated alkyl aromaticcompound with at least 2 times its weight of a suitable diluent, andthereafter passing the mixture through a reactor at a temperature of550° C. or greater and a pressure of between about atmospheric and 25 mmof mercury. Suitable diluents are generally substituted aromaticcompounds which are inert to the chloromethylated alkyl aromaticcompound and are stable at pyrolysis temperatures. Examples of suitablediluents are benzene, toluene, xylenes, chlorobenzenes, nitrobenzenes,methylbenzoates, phenyl acetate or diphenyl acetate. Preferred diluentsare the xylenes. Preferable temperatures are between about 700° C. and750° C. Preferable pressures are between about 35 and 25 mm of mercury.In a preferred embodiment, the reaction mixture is passed through a hottube packed with an inert material, for example, quartz chips orstainless steel helices. The product can be recovered by distillation.The product wherein the aromatic compound is benzene corresponds to theformula ##STR11## wherein R¹, R², R⁹ and c are as hereinbefore defined.

In the preferred embodiment wherein R⁹ is a hydrocarbyloxy carbonylmoiety, the hydrocarbyloxy carbonyl moiety can be converted to acarboxylate moiety by contacting the substituted (arylcyclobutene)compound with at least a molar equivalent of alkali metal hydroxide inan alkanol-water solvent system. In the embodiment wherein the aromaticradical is benzene, the product corresponds to the formula ##STR12##

Thereafter the carboxylate-substituted (arylcyclobutene) compound can beconverted to an acid chloride by contacting the carboxylate-substituted(arylcyclobutene) compound with thionyl chloride and refluxing at 70° C.to 80° C. The acid halide-substituted (arylcyclobutene) so formed can beused to prepare the novel monomers of this invention, as describedhereinafter. In the embodiment wherein the aryl radical is a benzenering, the product corresponds to the formula ##STR13##

In an alternative synthesis, an aryl compound with ortho dibromomethylgroups can be converted to a 1,2-diiodoarylcyclobutene, by contactingthe aryl compound substituted with ortho dibromomethyl moieties with analkali metal iodide in an alkanol solvent at reflux so as to form thediiodoarylcyclobutenes. The product can be recovered by filtering,evaporating the filtrate and recrystallizing the product. In theembodiment wherein the aryl radical is a benzene radical, the startingmaterial corresponds to the formula ##STR14## and theiodobenzocyclobutene corresponds to the formula ##STR15##

The 1,2-diiodoarylcyclobutenes can be converted to arylcyclobutenes bydissolving the 1,2-diiodoarylcyclobutenes in an alcohol solvent,preferably methanol or ethanol and contacting the solution with analkali metal hydroxide in the presence of a palladium-on-carbon catalystand H₂ gas at a temperature of 20° C. to 30° C. In general, at leastbetween about 2 and 4 moles of alkali metal hydroxide per mole of1,2-diiodoarylcyclobutene is used. Preferably, between about 50 and 200psi of hydrogen gas is used. The arylcyclobutenes prepared in thismanner can be recovered by distillation. In the embodiment wherein thearyl radical is a benzene radical, the product corresponds to theformula ##STR16##

The arylcyclobutene is thereafter brominated. In this process, thearylcyclobutene is dissolved in acetic acid and contacted with abrominating agent of pyridinium hydrobromide perbromide in the presenceof mercuric salts, for example, mercuric acetate, at a temperature ofbetween about 20° C. and 50° C. The brominated product can be recoveredby extraction and distillation. In the embodiment wherein aryl radicalis benzene, the product corresponds to the formula ##STR17##

The brominated arylcyclobutene can thereafter be carbonylated to preparea hydrocarbyloxy carbonyl-substituted arylcyclobutene. Thiscarbonylation is achieved by dissolving the brominated arylcyclobutenein an alkanol solvent, and thereafter contacting the solution withcarbon monoxide under pressure in the presence of a palladium catalyst,wherein the palladium is in the zero valence state, in the furtherpresence of an acid acceptor under conditions such that the brominatedarylcyclobutene compound undergoes carbonylation. Preferred catalystsare palladium acetate with a cocatalyst of triphenyl phosphine,palladium triphenyl phosphine tetrakis, and phenyl phosphine tetrakis,and bis(triphenyl phosphine) palladium chloride complex. The acidacceptor is generally a tertiary amine. In general, the reaction vesselis pressurized with carbon monoxide to a pressure of between atmosphericand 3000 psi, preferred pressures are between 600 and 1000 psi.

This process is preferably run at a temperature of between 100° C. and140° C., most preferably between 120° C. and 130° C. Thehydrocarbyloxycarbonyl arylcyclo-butene can be recovered by filteringoff the catalyst, washing away the acid scavenger with a 10 percentstrong acid solution, stripping off the solvent and distilling theproduct to purify it. To prepare a carboxamide-substitutedarylcyclobutene, a primary or secondary amine is substituted for thealcohol solvent. In the embodiment wherein the aryl radical is a benzeneradical, the process corresponds to the following equation: ##STR18##wherein R¹ and c are as hereinbefore defined and R⁶ and R¹⁰ arehydrocarbyl moieties. The hydrocarbyloxycarbonyl-substituted orcarboxamide-substituted arylcyclobutenes can thereafter be acidified andconverted to acid chlorides by the process described hereinbefore.

In another preparation of an arylcyclobutene, the reaction may followthat reported by Skorcz and Kaminski, Org. Syn., 48, pages 53-56 (1968).In a typical preparation, an alkyl cyanoacetate is added to a solutionof sodium metal in ethanol followed by the addition of anortho-halomethylaryl halide. The alkyl 2-(O-halomethylaryl)cyanoacetateis isolated and treated with aqueous sodium hydroxide. Subsequentacidification results in the cyanoacetic acid derivative. Thatderivative is placed into N,N-dimethylformamide and is refluxed to formthe 3-(O-halomethylaryl)propionitrile derivative which is isolated andadded to a suspension of sodamide in liquid ammonia. After anappropriate reaction time, ammonium nitrate is added and the ammoniaallowed to evaporate. The cyanoarylcyclobutene is isolated by etherextraction and purified by fractional distillation under reducedpressure.

Substituted arylcyclobutenes can be prepared by the same technique byusing the appropriately substituted reactants, such as an alkyl oralkoxybenzyl halide. Also substituents can result from using an alkylhaloacetate or a dialkylmalonate.

In another preparation based on the paper by Matsura et al., Bull. Chem.Soc. Jap., 39, 1342 (1966), o-aminoaryl carboxylic acids dissolved inethanol and hydrochloric acid added. Isoamylnitrite is slowly added tothe cold stirred solution and diethyl ether is then added. The product,aryldiazonium-2-carboxylate hydrochloride, is filtered. That product isplaced in a solvent, preferably ethylene dichloride, and acrylonitrileand propylene oxide is added to the stirred mixture which is then heatedunder nitrogen until the reaction is complete. After cooling, themixture is filtered and the product, 1-cyanoarylcyclobutene, is isolatedby fractionally distilling the filtrate under reduced pressure.

Amounts of reactants, reaction parameters and other details can be foundin the cited article, the examples of this application, or can be easilydeduced therefrom.

In a next sequence of reactions, the cyanoarylcyclobutene or substitutedderivative is nuclear substituted. In one preparation, thecyanoarylcyclobutene is added slowly to a cold solution of sodiumnitrate in concentrated sulfuric acid to form5-nitro-1-cyanoarylcyclobutene. That nitro compound is isolated,dissolved in ethanol and reduced by hydrogenation over a palladium oncarbon catalyst. The isolated product is 5-amino-1-cyanoarylcyclobutene.In the preferred embodiment where the aryl radical is benzene, theproduct corresponds to the formula ##STR19##

Cyclobutapyridines are prepared by the pyrolysis of 4-pyridyl propargylether at 550° C. See J. M. Riemann et al. Tetrahedron Letters, No. 22,pp. 1867-1870 (1977), incorporated herein by reference. Alternatively, apyridine-4-carbonitrile with an alkyl substituent on the carbon atomadjacent to the nitrile is reacted with sodium azide and ammoniumchloride in N,N-dimethylformamide to prepare a5(alkyl-4-pyridyl)tetrazole. The 5(alkyl-4-pyridyl)tetrazole ispyrolyzed at about 600° C. to prepare a cyclobutapyridine. See. W. D.Crow et al. Australian Journal of Chemistry 1741 et seq. (1975)incorporated herein by reference.

Amino cyclobutapyidines are prepared by reacting a cyclobutapyridinewith sodamide (NaNH₂) in N,N-dimethylaniline solvent at 110° C. Ahydroxycyclobutapyridine is prepared by reacting one mole of anaminocyclobutapyridine with one mole of sodium nitrite and two moles ofsulfuric acid in water at 0° C. for a period of time and thereafterwarming to 50° C. Halo-substituted cyclobutapyridine is prepared byreacting a hydroxypyridine in thionyl at reflux either neat or insolution, for example, thionyl chloride or thionyl bromide, inN,N-dimethylformamide solvent.

The N-substituted arylcyclobutenyl-unsaturated cyclic imides of thisinvention wherein the bridging member is a direct bond can be preparedby the following method. An unsaturated cyclic anhydride is contactedwith an amine-substituted arylcyclobutene under conditions so as to forman N-arylcyclobuteneylamido alkenoic acid. Such acid can thereafter bydehydrated to cyclize the amido alkenoic acid into a cyclic imide ringand form the N-substituted arylcyclobutenyl-unsaturated cyclic imide.

The formation of the arylcyclobutenyl amido alkenoic acid is achieved byreacting an unsaturated cyclic anhydride with an amine-substitutedarylcyclobutene. This reaction is exemplified in one preferredembodiment wherein the anhydride is maleic anhydride and thearylcyclobutene is 5-aminobenzocyclobutene, and is illustrated by thefollowing equation: ##STR20##

The cyclic anhydride and amino-substituted arylcyclobutene are contactedin a suitable solvent at a temperature of between -40° C. and 100° C.Suitable solvents include aliphatic hydrocarbons, aromatic hydrocarbons,ethers and halogenated hydrocarbons. It is preferred to run the processunder an inert atmosphere. It is also preferred to use freshly sublimedanhydride as any impurities in the anhydride can result in very pooryields. It is also preferred to use at least a 5 percent excess ofanhydride so as to drive the reaction to completion with respect to theamino-substituted arylcyclobutene compound.

Preferred temperatures are between 0° C. and 50° C. with between 20° C.and 25° C. being most preferred.

The N-arylcyclobutenylamido alkenoic acid can thereafter be dehydratedby one of two methods. In the preferred embodiment, theN-arylcyclobutenylamido alkenoic acid is contacted with a dehydratingagent in an aprotic reaction medium in the presence of a nickel II saltcatalyst. In general, the reaction medium is an aprotic solvent and caninclude ketones, ethers, amides or aliphatic halogenated hydrocarbons.Preferred reaction media include the ketones, with acetone being mostpreferred. The dehydrating agents include anhydrides, carbodiimides andisocyanates; with the anhydrides being preferred and acetic anhydridebeing most preferred.

The catalyst is any nickel II salt with nickel II acetate being mostpreferred. In general, between about 1 and 5 percent of the catalyst isuseful. It is preferable to run this process in the presence of anaprotic base such as a carbonate or tertiary amine, preferably atertiary amine. In general, between about 20 and 200 mole percent of atertiary amine is used, with between about 100 and 150 mole percentbeing preferred, wherein mole percentages are based on the startingN-arylcyclobutenylamido alkenoic acid. The mole ratio of the dehydratingagent to the N-arylcyclobutenylamido alkanoic acid is between about 4:1and 1:1, preferably between about 1.5:1 and 1:1.

It is preferred to run this process under an inert atmosphere.Temperatures which are useful are those at which the dehydration takesplace. Preferable temperatures are between about -20° C. and 100° C.,with between about 15° C. and 25° C. being most preferred.

In this reaction, the N-arylcyclobutenylamido alkenoic acid is notsoluble in the reaction medium but the cyclic imide product is soluble.The reactant is slurried in the reaction media and exposed to thereaction conditions described. The completion of the reaction is notedby dissolution of the reactants indicating formation of products.

In an alternative procedure, the N-arylcyclobutenyl amido alkenoic acidcan be dehydrated by dispersing the compound in a glacial acetic acidreaction media in the presence of an alkali or alkaline earth metalacetate salt, and heating the reaction mixture to a temperature at whichthe dehydration takes place to form the cyclic imide rings. Generally, asufficient amount of alkali or alkaline earth metal acetate salt tocause complete dehydration is suitable. Preferably, at least anequimolar amount of alkali or alkaline earth metal acetate salt is used,most preferably an-excess of 5 mole percent. The process can be run atany temperature at which the dehydration takes place, preferabletemperatures are between 50° C. and 140° C., with between about 100° C.and 120° C. being most preferred. Completion of the reaction isindicated by dissolution of the product.

In both instances, the product can be recovered by washing with waterand thereafter an aqueous solution of an inorganic base.

To prepare an N-substituted arylcyclobutenyl cyclic imide with ahydrocarbylene amido, hydrocarbyleneoxy or hydrocarbyleneoxycarbonylbridge, an unsaturated cyclic anhydride is reacted with a hydrocarbonsubstituted with amino and carboxyl moieties, for the hydrocarbyleneamido-bridged species, or a hydrocarbon substituted with amino andhydroxyl moieties, for the hydrocarbyleneoxy andhydrocarbyleneoxycarbonyl-bridged species, to prepare an amido alkenoicacid wherein the amido nitrogen is substituted with acarboxy-substituted hydrocarbyl or hydroxy-substituted hydrocarbylmoiety. This reaction can be performed at a temperature of between -40°C. and 100° C. in a suitable solvent. Suitable solvents includealiphatic hydrocarbons, aromatic hydrocarbons, ethers and halogenatedhydrocarbons. It is preferred to run the process under an inertatmosphere. It is preferred to use freshly sublimed anhydride as anyimpurities can result in very poor yields. It is preferred to use atleast a 5 percent excess of anhydride so as to drive the reaction tocompletion.

In the embodiment wherein the anhydride is maleic anhydride, thesereactions are exemplified by the following equations ##STR21## and##STR22## wherein R³ is as hereinbefore defined and R⁴ is ahydrocarbylene radical.

The amido alkenoic acid can be dehydrated using one of the twodehydration methods described hereinbefore so as to prepare aN-substituted cyclic imide wherein the substituent is aN-hydrocarbylcarbonyloxycarbonyl cyclic imide, or aN-hydrocarbylcarbonyloxy cyclic imide. In the embodiment wherein theN-substituted amido alkenoic acid was derived from maleic anhydride,this reaction is exemplified by the following equations ##STR23## and##STR24## wherein R³ and R⁴ are as hereinbefore defined and R⁵ is ahydrocarbyl moiety.

The N-hydrocarbylcarbonyloxycarbonyl cyclic imide is converted to ahydrocarbylene amido-bridged N-substituted arylcyclobutenyl cyclic imideby reacting the N-hydrocarbylcarbonyloxycarbonyl cyclic imide with anamino-substituted arylcyclobutene in the presence of a tertiary amineThis process can be accomplished by contacting the starting reactants ina chlorinated aliphatic hydrocarbon solvent at about 0° C. withagitation under an inert atmosphere. This process is exemplified by thefollowing equation ##STR25## wherein R⁴ and R⁵ are as hereinbeforedefined, and R⁶ is a hydrocarbyl radical.

To prepare a hydrocarbyleneoxy or hydrocarbyleneoxycarbonyl-bridgedN-substituted arylcyclobutenyl cyclic imide, theN-hydrocarbylcarbonyloxyhydrocarbyl cyclic imide is hydrolyzed toprepare a N-hydroxyhydrocarbyl cyclic imide. The hydrolysis is usuallyrun in an aqueous/alkanol solvent system in the presence of an acid orbase catalyst at between room temperature and reflux of the solventmixture (about 20° C. to 60° C.). This reaction is exemplified by thefollowing equation ##STR26## wherein R³, R⁴ and R⁵ are as hereinbeforedefined.

To prepare the hydrocarbyleneoxycarbonyl-bridged N-substitutedarylcyclobutenyl cyclic imides, the N-hydroxyhydrocarbyl cyclic imide isreacted with a chlorocarbonyl-substituted arylcyclobutene. In practice,the N-hydroxyhydrocarbyl cyclic imide is dissolved in a chlorinatedaliphatic hydrocarbon solvent to which is added a tertiary amine, whichfunctions as an acid acceptor, and thereafter thechlorocarbonyl-substituted arylcyclobutene in a chlorinated aliphatichydrocarbon is added slowly to the mixture. This is preferably done atabout 0° C. in an inert atmosphere. It is preferred to stir the reactionmixture for a period of time at 0° C. after the addition is complete.This reaction is exemplified by the following equation ##STR27## whereinR³, R⁴ and R⁶ are as hereinbefore defined.

The hydrocarbyleneoxy-bridged N-substituted arylcyclobutenyl cyclicimides can be prepared from the N-hydroxyhydrocarbyl cyclic imide in thefollowing manner. The N-hydroxyhydrocarbyl cyclic imide is reacted withp-toluene sulfonyl chloride and pyridine to prepare a cyclic imidohydrocarbyl p-toluene sulfonate. Either excess pyridine or methylenechloride are used as the solvent. The reactants are contacted inequimolar amounts, unless pyridine is the solvent, at a temperature ofbetween about 0° C. and 25° C. This reaction is exemplified by thefollowing equation ##STR28## wherein R³ and R⁴ are as hereinbeforedefined.

The cyclic imido hydrocarbyl p-toluene sulfonate is contacted with ahydroxy-substituted arylcyclobutene in the presence of a four to fivemolar excess of an alkali metal carbonate (such as potassium carbonate)based on the sulfonate, in a N,N-'dimethyl formamide solvent, to preparea hydrocarbyloxy-bridged N-substituted arylcyclobutenyl cyclic imide.This reaction takes place at temperatures of between about 20° C. and140° C. This process is exemplified by the following equation ##STR29##wherein R³ and R⁴ are as hereinbefore defined.

The hydrocarbylene amino-bridged N-substituted arylcyclobutenyl cyclicimides can be prepared by the following procedure. An amino-substitutedarylcyclobutene is reacted with about an equimolar amount of ahydrocarbon substituted with aldehyde and nitro moieties, in thepresence of between about 0.3 to 1.5 moles of sodium cyanoborohydride ina methanolic solvent at about 20° C. to about 25° C. The product isnitrohydrocarbyl amino-substituted arylcyclobutene. The process can beexemplified by the following equation ##STR30## wherein R⁴ is ashereinbefore defined and R⁷ is hydrogen or a hydrocarbyl moiety. Thenitro moiety on the nitrohydrocarbyl amino-substituted arylcyclobuteneis reduced to an amine moiety by contacting with an excess of metalliczinc in a concentrated hydrochloric acid solution at between about 20°C. and reflux. The product corresponds to the formula ##STR31## whereinR⁴ is as hereinbefore defined. The aminohydrocarbyl amino-substitutedarylcyclobutene is thereafter reacted with an unsaturated cyclicanhydride to prepare a hydrocarbylene amino-bridged N-arylcyclobutenylamido alkenoic acid. The conditions for this reaction are as describedhereinbefore for the reaction of an amino-substituted arylcyclobuteneand a cyclic anhydride. This reaction is exemplified by the followingequation ##STR32##

The hydrocarbylene amino-bridged N-aryl cyclobutenyl amido alkenoic acidis thereafter dehydrated by one of the methods described hereinbefore toprepare the hydrocarbylene amino-bridged N-substituted arylcyclobutenylcyclic imide. This product corresponds to the formula ##STR33## whereinR⁴ and R⁷ are as hereinbefore defined.

A hydrocarbylene-bridged N-substituted arylcyclobutenyl cyclic imide canbe prepared by the following procedure. A carboxy-substituted orcarbopxyhydrocarbyl-substituted arylcyclobutene is reduced to ahydroxyhydrocarbyl-substituted arylcyclobutene by reacting the startingmaterial with about a 3:1 molar excess of diborane in an ether or cyclicether solvent at between about 0° C. to 20° C. This process isexemplified by the following equation ##STR34## wherein R⁸ is a directbond or a hydrocarbylene moiety. The hydroxyhydrocarbyl-substitutedarylcyclobutene is reacted with a slight excess of thionyl chloride toprepare a chlorohydrocarbyl-substituted arylcyclobutene. The reactantsare usually contacted neat or in a methylene chloride solvent at atemperature of between about 0° C. and 50° C. An example of the productcorresponds to the formula ##STR35## The chlorohydrocarbyl-substitutedarylcyclobutene is thereafter reacted with about an equimolar amount ofpotassium phthalamide to prepare an N-arylcyclobutenylhydrocarbylphthalamide. The reactants are generally contacted near at temperaturesof between about 100° C. and 200° C. This reaction is exemplified by thefollowing equation ##STR36## wherein R⁸ is as hereinbefore defined. TheN-arylcyclobutenylhydrocarbyl phthalamide is reacted with about oneequivalent of hydrazine hydrate to prepare anaminohydrocarbyl-substituted benzocyclobutene. The reactants arecontacted in an alkanol solvent at the reflux of the solvent. Theproduct corresponds to the formula ##STR37## wherein R⁸ is ashereinbefore defined. The aminohydrocarbyl-substituted benzocyclobuteneis thereafter reacted with an unsaturated cyclic anhydride to prepare anN-hydrocarbylarylcyclobutenyl amido alkenoic acid under the conditionsdescribed hereinbefore. This process is exemplified by the followingequation ##STR38## wherein R³ and R⁸ are as hereinbefore defined. TheN-hydrocarbylarylcyclobutenyl amido alkenoic acid is then dehydrated toform a cyclic imide ring thus preparing an N-hydrocarbylarylcyclobutenylcyclic imide. This process is performed using one of the two dehydrationprocesses described hereinbefore.

To prepare a mercaptoarylcyclobutene, an arylcyclobutene sulfonic acidand equimolar amounts of sodium hydroxide are contacted in aqueoussolution at about 20° C.-25° C. to prepare sodium arylcyclobutenesulfonate. The sodium arylcyclobutene sulfonate is dried at 100° C., andthereafter contacted in neat form with about 0.48 mole of phosphorouspentachloride at about 170° C. to 180° C. to prepare an arylcyclobutenesulfonyl chloride. The arylcyclobutene sulfonyl chloride is reduced withzinc, about 4.9 moles, in the presence of about 6.8 moles ofconcentrated sulfuric acid at about 0° C. to prepare themercaptoarylcyclobutene.

To prepare the alkylenethio-bridged N-substitutedarylcyclobutenyl-unsaturated cyclic imide, equimolar amounts of amercapto arylcyclobutene, sodium hydroxide and a dihaloalkane arecontacted in an alkanol solvent at between about 0° C. and 50° C. Theproduct is a haloalkyl-substituted arylcyclobutenyl sulfide. Thisreaction is exemplified by the following equation ##STR39## wherein X ishalogen and R⁴ is a divalent alkane radical. Two moles of thehaloalkyl-substituted arylcyclobutenyl sulfide is contacted with about0.8 moles of potassium phthalimide and about 0.4 mole of potassiumcarbonate. The reactants are contacted neat at a temperature of about190° C. to prepare an n-phthalimidoalkyl arylcyclobutenyl sulfide. Thisprocess is exemplified in one preferred embodiment by the followingequation ##STR40##

The phthalimidoalkyl arylcyclobutenyl sulfide is contacted with ahydrazine hydrate in a mole ratio of about 1 to 1.25, respectively, inan alkanol solvent at reflux to prepare an aminoalkyl arylcyclobutenylsulfide. In one preferred embodiment, the product corresponds to theformula ##STR41##

The aminoalkylarylcyclobutenyl sulfide is then reacted with anunsaturated cyclic anhydride to prepare a thioalkylene-bridged N-arylcyclobutenyl aminoalkenoic acid. This is achieved under conditionsdescribed hereinbefore. Thereafter, the alkylenethio N-arylcyclobutenylamidoalkenoic acid can be dehydrated by one of the methods describedhereinbefore to prepare an alkylenethiobridged N-substitutedarylcyclobutenyl cyclic imide.

To prepare arylenethio-bridged N-arylcyclobutenyl cyclic imide,equimolar amounts of a mercapto arylcyclobutene, sodium hydroxide and ahalonitro-substituted aromatic compound are contacted in an alkanolsolvent under reflux to prepare a nitroaryl arylcyclobutenyl sulfide.The nitro group on the nitroaryl arylcyclobutenyl sulfide is reduced bycontacting one mole of such compound with about two moles of tin andabout six moles of concentrated hydrochloric acid to prepare anaminoaryl arylcyclobutenyl sulfide. The aminoaryl arylcyclobutenylsulfide is thereafter contacted with a an unsaturated cyclic anhydridein equimolar amounts in methylene chloride at a temperature of about 0°C. to about 25° C. to prepare an arylenethio-bridged N-arylcyclobutenylamidoalkenoic acid. The arylenethio-bridged N-arylcyclobutenylamidoalkenoic acid is dehydrated using procedures described hereinbeforeto prepare an arylenethio-bridged N-arylcyclobutenyl cyclic imide.

The hydrocarbylenethio-bridged N-arylcyclobutenyl cyclic imides can becontacted with equimolar amounts of peracetic acid in an ethyl acetatesolvent at between about 0° C. to 20° C. to prepare ahydrocarbylenesulfinyl-bridged N-arylcyclobutenyl cyclic imide. Thehydrocarbylenethio-bridged N-arylcyclobutenyl cyclic imide can becontacted with about 2 moles of peracetic acid for each mole of thebridged cyclic imide in ethyl acetate solvent at about 0° C. to 20° C.to prepare a hydrocarbylenesulfonyl-bridged N-arylcyclobutenyl cyclicimide.

To prepare the various bridged N-arylcyclobutenyl cyclic imides whereinthe aryl moiety is a heterocycle, the appropriately substitutedheterocyclic N-arylcyclobutenyl cyclic imide is reacted in the mannerdescribed herein to get the appropriately desired compound.

The compounds of this invention are unique in several respects. Theyhave intramolecular diene and dienophile functionality. They arethermally stable for long periods at elevated temperatures, up to 100°C. They are readily polymerizable. The compounds of this invention areuseful in the preparation of polyimides by polymerization of one or moreof the compounds of this invention. It is believed that thepolymerization takes place by a Diels-Alder reaction wherein theunsaturation on the cyclic imide acts as a dienophile while thecyclobutene ring forms a diene which reacts with the dienophile to formthe polymeric compositions.

The polymers of this invention are prepared by heating the compoundsdescribed hereinbefore to a temperature of 170° C. or greater.Preferable temperatures for polymerization are 200° C. or greater. Ingeneral, it is preferable to run the polymerization at a temperature ofbetween about 170° C. and 300° C., with between about 200° C. and 300°C. being most preferred.

Wherein the N-substituted arylcyclobutenyl cyclic imides correspond tothe formula ##STR42## wherein Ar, R¹, R², R³, Y and a are as describedhereinbefore; it is believed that the polymeric composition containsunits which correspond to the formula ##STR43##

It is further believed that in one preferred embodiment the polymersderived from monomers of such a formula result in the preparation ofpolymers which correspond generally to the formula ##STR44## wherein Ar,R¹, R², R³, Y and a are as described hereinbefore and c is a real numberof about 2 or greater, and most preferably 20 or greater.

In another preferred embodiment, the polymeric composition is thepolymer of one or more compounds which corresponds to the formula##STR45## wherein R¹, R², R³, Y and b are as hereinbefore defined. Inthis embodiment, it is believed that the polymer prepared contains unitswhich correspond to the formula ##STR46## wherein R¹, R², R³, Y and bare as hereinbefore defined.

In one preferred embodiment wherein the compound or compoundspolymerized corresponds to said formula, it is believed that the polymerprepared corresponds to the formula ##STR47## wherein R¹, R², R³, Y areas hereinbefore defined, and d is a real number of about 2 or greater. dis preferably about 20 or greater.

The novel N-substituted arylcyclobutenyl-unsaturated cyclic imidecompounds of this invention are useful in the preparation of polymericcompositions. In general, these polymeric compositions are prepared bycontacting these N-substituted arylcyclobutenyl-unsaturated cyclic imidecompounds and heating them to the polymerization temperature of theparticular monomer used. The polymerization is in additionpolymerization wherein no volatiles are generated. Furthermore, nocatalyst initiator or curing agents are necessary for the polymerizationto take place. It is believed that the polymerization takes place whenthe cyclobutene ring undergoes transformation to prepare an aryl radicalwith two olefinic unsaturated moieties ortho to one another wherein theolefinic unsaturated moieties thereafter undergo reaction with theunsaturated cyclic imide moieties. It is to be noted that thetemperature at which polymerization is initiated is dependent upon thenature of substituents on the cyclobutene ring. In general, wherein thecyclobutene ring is unsubstituted, the polymerization is initiated atabout 200° C. Wherein the cyclobutene ring is substituted with anelectron-donating substituent, the polymerization temperature isgenerally lowered, the higher the ability of the substituent to donateelectrons, the lower the polymerization initiation temperature is.

The method of polymerization of the N-substitutedarylcyclobutenyl-unsaturated cyclic imide monomers has a significanteffect on the nature and properties of the polymeric compositionprepared. In one embodiment, the N-substitutedarylcyclobutenyl-unsaturated cyclic imide monomers of this invention canbe melt polymerized. The melt polymerization of N-substitutedarylcyclobutenyl-unsaturated cyclic imide monomers allows their use inthe preparation of solid parts, as coatings, in composites, as adhesivesand as fibers.

In one embodiment of the melt polymerization, the monomers are heated tothe temperature at which it melts, preferably this is a temperature ofbetween about 80° C. and 100° C., and thereafter poured or injected intoa mold. Thereafter, pressure may be applied on the melted monomer in themold. Generally, pressures of between about atmospheric and 2000 psi aresuitable. Thereafter, the monomer is heated to a temperature at whichthe monomers undergo polymerization. This is preferably a temperature ofbetween about 200° C. and 300° C., more preferably between about 200° C.and 250° C. for between about 10 minutes and 3 hours. Upon cooling, thepolymerized composition can be removed from the mold.

Polymers prepared in this manner can subsequently be thermally treatedat temperatures above 200° C. to raise the modulus and lower thecoefficient of expansion of such polymeric compositions.

In general, the polymers prepared by this method are insoluble in thatthey swell but do not dissolve, are thermally stable at 200° C., have agood modulus, a low water pickup and are reasonably hard.

In another embodiment, the N-substituted arylcyclobutenyl-unsaturatedcyclic imide monomers of this invention can be used to prepare coatingsand films. In such embodiments, the monomers are dissolved in a suitablesolvent and coated onto the substrate of choice, and thereafter thecoated substrate is exposed to temperatures at which the monomersundergo polymerization over a period of time sufficient for thepolymerization to go to completion. Under preferable conditions,temperatures of above about 200° C. for between 1 and 5 hours are used.Suitable solvents are those which volatilize away at temperatures belowthe polymerization temperature. Preferred solvents are cyclic andaliphatic ethers, lower alkanols, amides, and chlorinated hydrocarbonsolvents. It is preferable to saturate the solvent with the monomer, a20 to 30 weight percent concentration of monomer in the solvent ispreferred.

The N-substituted arylcyclobutenyl-unsaturated cyclic imide monomers maybe combined with the powder-form or fibrous fillers or reinforcingmaterials either before or after heat treatment. For example, it ispossible to impregnate powder-form or fibrous fillers or reinforcingmaterials such as quartz sand or glass cloths, with the N-substitutedarylcyclobutenyl-unsaturated cyclic imide monomers, optionally insolution.

Suitable fillers and reinforcing materials are, generally, in any powderform and/or fibrous products, for example, of the type commonly used inthe production of moldings based on unsaturated polyester resins orepoxide resins. Examples of products such as these are, primarily,granular fillers such as quartz powder, ground shale, asbestos powder,powdered corundum, chalk, iron powder, aluminum powder, sand, gravel andother fillers of this kind, also inorganic or organic fibers, moreespecially glass fibers in the usual textile forms of fibers, filamentsrovings, yarns, nonwovens, mats and cloths, etc. In this connection,amino silane-based finishes have proven to be particularly effective. Itis also possible to use corresponding textile structures of organic,preferably synthetic fibers (polyamides, polyesters) or on the basis ofquartz, carbon, metals, etc., as well as monocrystals (whiskers).

The end products combined with fillers or reinforcing materials may beused in particular in vessel and pipe construction by the windingtechnique, in electrical engineering, in mold construction and toolmaking and also in the construction of heavily stressed components, inthe lightweight construction of vehicles in aeronautical andastronautical engineering.

In another embodiment, the N-substituted arylcyclobutenyl-unsaturatedcyclic imide monomers can be used as adhesives. In such embodiment, oneof the substrates to be joined is contacted with some form of themonomers, for example, the monomer in a powdered form. Thereafter, thesecond substrate to be adhesivated is contacted with the substratepreviously contacted with the monomer where the monomer was contactedwith the first substrate. Thereafter, pressure of at least 1 psi isapplied and the monomers and substrates are raised to a temperature atwhich the monomer undergoes polymerization.

In one embodiment, the N-substituted arylcyclobutenyl-unsaturated cyclicimide monomers can be formed into a prepolymer which thereafter can bepolymerized. To form the prepolymer, the N-substitutedarylcyclobutenyl-unsaturated cyclic imide monomers are contacted in aninert atmosphere or under vacuum and heated to a stage at which thepolymerization mixture is sufficiently viscous enough to be moldable inconventional molding equipment. In general, the monomers can becontacted at a temperature of 190° C. to 220° C. for between about 1 and10 minutes. Thereafter, the prepolymer can be used in various techniquesto prepare the polymeric compositions of this invention. In onepreferred embodiment, the prepolymer is cooled to form a powder whichcan be used to form compression molded articles, as an adhesive, and inmany other uses. In another embodiment, a prepolymer of theN-substituted arylcyclobutenyl-unsaturated cyclic imide monomers can beprepared by precipitation polymerization. In particular, the techniqueinvolves heating such monomers in a solvent to prepare a low molecularweight prepolymer that contains unreacted arylcyclobutene rings. Asolvent is used which dissolves the monomer but not the prepolymer. Asthe prepolymer forms, it precipitates and is removed. The prepolymer canbe fabricated in a hot compression mold which reacts out the remainingarylcyclobutene rings to give a thermoset polymer. The product is a finewhite powder.

Preferable solvents are nonpolar solvents, such as aromatichydrocarbons, aliphatic hydrocarbons, aliphatic chlorinatedhydrocarbons, aromatic chlorinated hydrocarbon solvents, biphenols,naphthalenes or polychlorinated biphenols. The polymerization can takeplace at temperatures generally of between about 200° C. and 240° C. forperiods of between about 1 and 5 hours. In general, the monomer can bedissolved up to saturation in the solvent used. A 20 to 30 percent byweight solution of the monomer in the solvent is preferred.

In another embodiment, the N-substituted arylcyclobutenyl-unsaturatedcyclic imide monomers can be polymerized by solution polymerizationtechniques. In this embodiment, the monomers are dissolved in dipolaraprotic solvents with boiling points above the polymerizationtemperature of the monomers It is preferable that the solvents have aboiling point of above 200° C. and more preferable that the solventshave a boiling point of above 250° C. Examples of preferred dipolaraprotic solvents include amides and sulfones. It is necessary to add tothe solution lithium salts which solubilize the monomer in the solvents,preferably between about 5 and 20 weight percent based on the monomer. Apreferred lithium salt is lithium chloride. The polymerization takesplace by heating the polymerization solution to a temperature at whichthe monomer undergoes polymerization, preferably above 200° C. Thepolymerization time is generally between about 1 and 10 hours. Thepolymer can be recovered by adding water to precipitate the polymer fromthe reaction solution and thereafter stripping off the solvent. Thepolymers prepared with this method can be used in compression moldingsor to prepare coatings. It is often desirable to process these polymersunder elevated temperatures.

In another embodiment, the monomers of this invention which undergopolymerization at a temperature which is below the melting point of themonomer can be polymerized in a solid state polymerization. In thismethod, the monomers are heated to a temperature at which polymerizationtakes place Polymers prepared in this method can be useful in thepreparation of bearings, seals and other parts by powder metallurgytechniques.

Specific Embodiments

The following examples are included to illustrate the invention, and donot limit the scope of the invention or the claims Unless otherwisespecified, all parts and percentages are by weight.

EXAMPLE 1 (a) Preparation of Ethyl 2-(o-Chlorobenzyl) Cyanoacetate

Into a 3-liter, three-necked flask equipped with a mechanical stirrer,reflux condenser, addition funnel and nitrogen inlet is placed asolution of 35.64 g (1.55 moles) of sodium metal in 1050 mm of absolute2B ethanol. The solution is stirred under nitrogen and cooled to 0° C.in an ice bath and 763.56 g (6.75 moles) of ethyl cyanoacetate is addeddropwise over a period of 15 minutes. To this white suspension is added241.56 g (1.5 moles) of o-chlorobenzyl chloride dropwise over 1 hour.After the addition is complete, the ice bath is removed and the mixtureis slowly heated under nitrogen to reflux and held there for 3 hours.The resulting pink-colored mixture is allowed to cool under nitrogenovernight at room temperature. About 1 liter of ethanol is distilledfrom the reaction mixture and 1.5 liters of water are added. The organiclayer is taken up in three 400-ml portions of methylene chloride, andthe solutions are combined and washed once with 150 ml of water. Themethylene chloride solution is dried over anhydrous magnesium sulfate,filtered and evaporated on a rotary evaporator. The residual liquid isdistilled under reduced pressure through an insulated 12-inch Vigreuxcolumn. A forerun of ethyl cyanoacetate (boiling point 55° C.-60° C./0.3mm Hg) comes over first followed by pure ethyl2-(o-chlorobenzyl)cyanoacetate. The infrared, 'H and ¹³ C nuclearmagnetic resonance are used to establish the structure. The yield is 68percent of product having a boiling point of 130° C.-135° C./0.3 mm Hg.

(b) Preparation of 2-(o-Chlorobenzyl)Cyanoacetic Acid

In a 2-liter, three-necked flask equipped with a mechanical stirrer,addition funnel and nitrogen inlet is placed 243 g (1.02 moles) of ethyl2-(o-chlorobenzyl)cyanoacetate. A solution of 54.52 g (1.363 moles) ofsodium hydroxide pellets and 545 ml of water is added over a period of15 minutes while stirring under nitrogen. Initially, the solution turnscloudy and then becomes clear. The resulting mixture is stirred for 5hours at room temperature under nitrogen. Water (445 ml) is added andthe mixture is cooled in an ice bath. Acidifying to pH 1 with 4Nhydrochloric acid gives a fine white precipitate that is filtered andwashed with water until neutral to litmus. The product is dried in avacuum oven at 60° C. overnight to yield 20 g (97 percent) of whitepowder. This material is recrystallized from toluene to give pure whitecrystals of 2-(o-chlorobenzyl)cyanoacetic acid identified by infrared,'H and ¹³ C nuclear magnetic resonance. The yield is 94 percent ofproduct having a melting point of 132° C.-134° C.

(c) Preparation of 3-(O-chlorophenyl) propionitrile

Into a 1-liter, three-necked flask equipped with a mechanical stirrer,reflux condenser and nitrogen inlet is placed 138.5 g (0.66 mole) of2-(o-chlorobenzyl)cyanoacetic acid and 220 ml of dryN,N-dimethylformamide. The mixture is stirred and slowly heated undernitrogen to reflux and held there for 6 hours. The resulting yellowmixture is allowed to cool under nitrogen overnight at room temperature.A precipitate (approximately 0.5 g) that forms is filtered off and thefiltrate is poured into 1 liter of water. The organic layer is taken upin three 330-ml portions of ethyl ether/hexane (1:1 v/v), and thesolutions are combined and washed once with 150 ml of water. The ethylether/hexane solution is dried over anhydrous magnesium sulfate,filtered and evaporated on a rotary evaporator The residual liquid isdistilled under reduced pressure through an insulated 12-inch Vigreuxcolumn with the product being collected at 82° C.-85° C./0.3 mm Hg as acolorless liquid identified by infrared, 'H and ¹³ C nuclear magneticresonance. The yield is 94.7 percent.

(d) Preparation of 1-Cyanobenzocyclobutene

A 3-liter, three-necked flask equipped with a dry ice condenser,mechanical stirrer and Claisen adapter fitted with an ammonia gas inletand nitrogen inlet is rinsed with acetone, dried in an oven at 125° C.,and heated with an air gun while flushing with nitrogen. The apparatusis cooled in a dry ice-acetone bath and the condenser is filled with adry ice-acetone mixture. Ammonia gas flow is initiated and 600 ml iscondensed out. The ammonia inlet tube is replaced by a stopper, and 0.4g of powdered iron (III) nitrate is added. Sodium metal, 51.52 g (2.24moles) is added in small portions over 1 hour. After all the sodium isadded, the dry ice bath is removed and cooling is left to the dry icecondenser. Complete conversion of the sodium/ammonia solution tosodamide is indicated by a color change from deep blue to gray. Next,92.82 g (0.56 mole) of 3-(o-chlorophenyl)propionitrile is added over aperiod of 10 minutes. The last traces of the nitrile are washed into theflask with small amounts of anhydrous ethyl ether. The dark greenreaction mixture is stirred vigorously for 3 hours and then is treatedwith 134.4 g (1.68 moles) of solid ammonium nitrate. The ammonia isallowed to evaporate overnight at room temperature. Water (420 ml) iscautiously added to the residue. The organic layer is taken up in two224-ml portions of chloroform, and the solutions are combined and washedtwice with 140 ml of aqueous 5 percent hydrochloric acid and once with140 ml of water. The chloroform solution is dried over anhydrousmagnesium sulfate, filtered, and evaporated on a rotary evaporator. Theresidual liquid is distilled under reduced pressure through an insulated12-inch Vigreux column. The product is collected at 59° C.-69° C./0.2 mmHg. The infrared, 'H and ¹³ C nuclear magnetic resonance are run toidentify the product. The yield is 50 percent.

(e) Preparation of 5-nitro-1-cyanobenzocyclobutene

Into a 500-ml, three-necked flask equipped with an addition funnel,thermometer and nitrogen inlet is placed 14.1 g (0.17 mole) of sodiumnitrate and 135 ml of concentrated sulfuric acid. The mixture is stirredunder nitrogen while cooling to -5° C. (calcium chloride/ice) and 19.5 g(0.16 mole) of 1-cyanobenzocyclobutene is added dropwise at such a rateas to keep the reaction temperature below 2° C. The reaction mixture isthen stirred under nitrogen at 0° C.-5° C. for 0.5 hour, poured onto1050 g of ice, and extracted with four 300-ml portions of methylenechloride. The methylene chloride solutions are combined, washed withfour 150-ml portions of 10 percent sodium bicarbonate, once with 300 mlof water, and dried over anhydrous magnesium sulfate. The methylenechloride solution is filtered and evaporated on a rotary evaporator togive 26.9 g of residue which is recrystallized from absolute 2B ethanolto give pure 5-nitro-1-cyanobenzocyclobutene identified by infrared, 'Hand ¹³ C nuclear magnetic resonance. The melting point is 110° C.-112°C. and the yield is 64.1 percent.

(f) Preparation of 5 -Amino-1-Cyanobenzocyclobutene

Into a 1-liter, three-necked flask equipped with a gas dispersion tube,reflux condenser, rubber septum and nitrogen inlet is placed 7 g (0.04mole) of 5-nitro-1-cyanobenzocyclobutene and 400 ml of absolute 2Bethanol. The mixture is stirred under nitrogen and heat is applied todissolve the solid. After adding 2.4 ml of glacial acetic acid and 1.6 gof 5 percent palladium on carbon, hydrogen flow is initiated and themixture is hydrogenated at atmospheric pressure and ambient temperature.The hydrogenation is followed by thin-layer chromatography (silica gel;70 percent toluene, 25 percent ethyl acetate, 5 percent triethylamine aseluent) and this shows the reaction is essentially complete in 1 hour.After 3 hours, the hydrogen flow is stopped and the system is purgedwith nitrogen for 15 minutes to remove excess hydrogen gas. The catalystis removed by filtration using Celite and quickly quenched in water. Thefiltrate is evaporated to dryness on a rotary evaporator and the residueis treated with aqueous 10 percent sodium hydroxide. The aqueoussolution is extracted with three 100-ml portions of ethyl ether, and thesolutions are combined and washed once with 100 ml of water. The ethylether solution is dried over anhydrous potassium carbonate, filtered andevaporated on a rotary evaporator to give an amber-colored oil thatsolidified on standing. The product is pumped under vacuum overnight toremove the last traces of ethyl ether and stored under nitrogen. Theinfrared, 'H and ¹³ C nuclear magnetic resonance are run. The yield is86.4 percent.

(g) Preparation of N-[5-(1-Cyanobenzocyclobutenyl)]maleamic Acid

Into a 250-ml, three-necked flask equipped with a mechanical stirrer,addition funnel, reflux condenser, thermometer and nitrogen inlet isplaced 4.9 g (0.05 mole) of freshly sublimed maleic anhydride and 50 mlof dry chloroform. The mixture is stirred under nitrogen while coolingto 15° C. in an ice bath and a solution of 7 g (0.05 mole) of5-amino-1-cyanobenzocyclobutene in 50 ml of dry chloroform is addeddropwise at such a rate as to keep the reaction mixture below 20° C. Thereaction is maintained below 20° C. and stirred under nitrogen for 1hour after addition is complete. The solidN-[5-(1-cyanobenzocyclobutenyl)]maleamic acid is filtered off, washedwith cold chloroform, then with hot ethyl acetate/2B ethanol (absolute;1:1 v/v), and dried overnight in a vacuum oven at 60° C. The infrared,+H and ¹³ C nuclear magnetic resonance, and carbon, hydrogen, nitrogenanalyses are run.

    ______________________________________                                        Analysis       Calculated                                                                              Found                                                ______________________________________                                        carbon         64.46     63.80                                                hydrogen       4.16      4.44                                                 nitrogen       11.57     11.36                                                ______________________________________                                    

The yield is 11.32 g equal to 94.25 percent and the melting point is190° C.-192° C.

(h) Preparation of N-[5-(1-Cyanobenzocyclobutenyl)]maleimide

Into a 250-ml, three-necked flask equipped with a mechanical stirrer,reflux condenser, thermometer and nitrogen inlet is placed 11 g (0.045mole) of N-[5-(1-cyanobenzocyclobutenyl)]maleamic acid, 2.4 g (0.03mole) of anhydrous sodium acetate, and 45.94 g (0.765 mole) of freshglacial acetic acid. The mixture is stirred and slowly heated undernitrogen until a clear yellow solution results (117° C.-118° C.). After5 minutes the heat is removed and the reaction mixture is allowed tocool under nitrogen overnight at room temperature. It is then slowlypoured into a vigorously stirred slurry of ice and water (120 g total),and the resulting yellow precipitate filtered, washed with water untilneutral to litmus, and transferred to a 500-ml beaker containing 150 mlof aqueous saturated sodium bicarbonate. This mixture is stirred for 10minutes, then 150 ml of chloroform is added and stirred for anadditional 10 minutes. The organic layer is taken up in three 50-mlportions of chloroform, and the solutions are combined and washed oncewith 150 ml of water. The chloroform solution is dried over anhydrousmagnesium sulfate, filtered and evaporated on a rotary evaporator togive a viscous yellow oil. The product is pumped under vacuum overnightto give a yellow solid that is purified by column chromatography onsilica gel using 70 percent toluene/30 percent ethyl acetate as theeluent. The infrared, +H and ¹³ C nuclear magnetic resonance, andcarbon, hydrogen, nitrogen analyses are run.

    ______________________________________                                        Analysis       Calculated                                                                              Found                                                ______________________________________                                        carbon         69.60     69.30                                                hydrogen       3.60      3.70                                                 nitrogen       12.50     12.34                                                ______________________________________                                    

The yield is 5.7 g equal to 56.5 percent. The melting point is 55°C.-60° C.

EXAMPLE 2

In a one-liter, one-necked, flask dispersed with nitrogen is placed 10 g(0.413 mole) of maleamic acid, 8.57 g (0.0840 mole) of acetic anhydride,0.2314 g (0.0013 mole) of nickel (II) acetate, 429 ml of acetone and 8.6ml (6.24 g) of triethylamine. This solution is stirred under nitrogenfor about 64 hours. Stirring is stopped and the solution is poured into300 ml of water saturated with sodium carbonate. Chloroform (150 ml) isadded to extract the organic layer. The sodium carbonate comes out ofsolution, collecting in the bottom of the separatory funnel Extra wateris added to the contents in the funnel to redissolve the sodiumcarbonate. The organic layer is then extracted and two 150-ml chloroformextractions are performed. The three chloroform extractions are combinedand washed with 300 ml of water, dried over magnesium sulfate, filteredand rotovaped. A yellowish-brown oil is obtained and dried under vacuumfor about 16 hours to remove remaining chloroform. Using a column packedwith silica gel and a solvent of 70 percent toluene, 30 percentethylacetate, the product is chromatographed. The combined samplescontaining the product (found by TLC) are rotovaped and pumped undervacuum for about 16 hours. Yield is 8.97 g of product.

EXAMPLE 3 Preparation of Poly-N-[5-(1-cyanobenzocyclobutenyl)]maleimide

Into a 25-ml, two-necked flask equipped with a reflux condenser,nitrogen inlet and magnetic stir bar is placed 0.5 g (2.2 mmole) ofN-[5-(1-cyanobenzocyclobutenyl)]maleimide and 15 ml of mesitylene. Themixture is purged with nitrogen and heated with stirring. Initially, allof the maleimide derivative dissolves to give a clear yellow solution.Upon reaching reflux, the solution becomes cloudy and a beige powderprecipitates. After 2 hours of reflux, the reaction is cooled and theprecipitated polymer is filtered off and washed free of residualmesitylene with chloroform and dried. The yield is quantitative.

EXAMPLE 4

Into a 25-ml, one-necked, round-bottomed flask equipped with a nitrogeninlet is placed 0.1 g (0.446 mmole) ofN-[5-(1-cyanobenzocyclobutenyl)]maleimide. The flask is purged withnitrogen and immersed in an oil bath. The bath temperature is raised to200° C. over 1 hour. After heating at 200° C. for 20 minutes, the meltedmonomer solidifies to a pale yellow transparent solid. The flask iscooled and the polymer removed by breaking it up with a spatula Theyield is quantitative.

EXAMPLE 5 Preparation of 4-Nitrophenyl-4-Benzocyclobutenyl Ketone

Into a 100 ml roundbottom one neck flask equipped with a magneticstirring bar, a reflux condensor and a nitrogen inlet is placedbenzocyclobutene 10 g(96.15 mmol) and 4-nitrobenzoyl chloride 11.9g(64.2 mmol). To the flask is added Fe₂ O₃ (0.65 mmol, 1 mol %). Theflask is heated to 150° C. under a nitrogen atmosphere with vigorousstirring overnight. The mixture is cooled to room temperature, mixedwith chloroform (120 ml) and transferred to a separatory funnel. Thedark brown solution is washed with 10 percent aqueous sodium bicarbonate(50 ml) twice, water (50 ml) and brine (50 ml) each once. The solutionis dried over magnesium sulfate overnight and filtered through celite.The volatiles are removed on a rotovap to give a deep red-black viscousliquid. The liquid is contacted with 100 ml of n-hexane and heated toboiling. The hot n-hexane is decanted away from the undissolved brownliquid. The hexane treatment is repeated three more times. The resultantyellow n-hexane layers are combined and slowly cooled to roomtemperature. An off-white solid (rosettes) precipitates out of solution.The solid is isolated by suction filtration. The filtrate isconcentrated to one half of its volume and allowed to stand. The solidrecovered has a weight of 4.8 grams (a 30 percent yield). NMR and IRspectra are taken of the solid and the spectra agree with the structureof 4-nitrophenyl-4-benzocyclobutenyl ketone.

EXAMPLE 6 Preparation of 4-Aminophenyl-4-Benzocyclobutenyl Ketone

Into a 250 ml three neck round bottom flask equipped with a magneticstirring bar, a reflux condensor with a nitrogen inlet and a thermometerand an equilibrating addition funnel is charged 1.0 g (3.95 mmol) of4-nitrophenyl-4-benzocyclobutenyl ketone, 4.46 g (19.75 mmol) of (SnCl₂9.2H₂ O) and 100 ml of ethanol. Under a nitrogen atmosphere, the mixtureis heated to 60° C. To the mixture, in a slow dropwise manner is addedsodium borohydride, 75 mg (1.975 mmol) in 20 ml of ethanol, over aperiod of 20 minutes. After the addition, the temperature of the mixtureis maintained at 60° C. for 30 minutes. The mixture is cooled to 10° C.and 80 ml of water previously chilled is added. Concentrated sodiumhydroxide is added until the pH is 7 (4M, NaOH, about 6 ml). The mixtureis transferred to a 500 ml round-bottom flask and the ethanol is removedon a rotovap. Thereafter, 100 ml of water is added to the off-whileslurry and the aqueous phase is extracted with diethyl ether four timeswith 100 ml aliquots. The ether extracts are dried over sodium sulfateovernight. The sodium sulfate is filtered from the diethyl etherextracts and the diethyl ether is removed on a rotovap. A bright orangesolid (0.87 g) is obtained. The solid is recrystallized using carbontetrachloride (200 ml) and decolorizing charcoal. The first crop ofcrystals is a pale yellow solid 0.54 g (61.3%). The carbon tetrachlorideis concentrated to 50 ml and left standing overnight. NMR and IRindicate the product is 4-aminophenyl-4-benzocyclobutenyl ketone.

EXAMPLE 7 The Preparation of ##STR48##

Into a 100 ml round bottom flask equipped with a magnetic stirring barand a nitrogen inlet is placed 1.0 g(4.482 mmol) of4-aminophenyl-4-benzocyclobutenyl ketone and 20 ml of acetone. To thesolution is added 4.40 g(4.482 mmol) of maleic anhydride in severalportions over two minutes, with stirring. The solution is stirred atroom temperature for two days. A white solid precipitates. The whitesolid is believed to be ##STR49## The white solid and the solutiondescribed above are stirred with 4.9 mg(8.955 mmol, 0.85 ml) of aceticanhydride, 35 mg(0.142 mmol) of hydrated sodium acetate (four waters ofhydration) and 19 drops of triethyl amine. As the triethyl amine isadded, the solution turns yellow. Stirring at room temperature iscontinued overnight. The reaction mixture is an orange hazy mixture(fine solid is present). The reaction mixture is poured into 80 ml ofvigorously stirred aqueous sodium bicarbonate. An orange solidprecipitates from the solution. To the solution is added 100 ml ofchloroform, and the solution is transferred to a separatory funnel. Thelayers are separated and the aqueous phase is extracted with 100 ml ofchloroform. The chloroform extracts are combined and washed with 50 mlof water, and then 50 ml of brine. The solution is dried over magnesiumsulfate and the suction filtered through celite. The solvent is removedby a vacuum to give 1.20 g of an orange viscous syrup. The product isrecrystalized using ethanol and decolorizing charcoal. The mixture isgravity filtered to give a pale yellow solution. The solution isconcentrated to one-half its volume and placed in ice. A white solidprecipitates. The solution is allowed to stand overnight. The solid isisolated and dried in air for 1 hour. The weight of the product is, andhas a 0.49 g melting point of 138°-139° C. Another 0.39 g of product isfurther isolated to give a total yield of 0.88 g. The product isexamined by IR and NMR and shows agreement with the following structure,##STR50## The DSC of the product indicates a melting point of 147° C.and an exotherm is observed at 260.4° C. The energy of the exotherm is347 J/g. A rescan of the DSC shows no melting point or exotherm but doesexhibit a T₂ at 260.4° C.

EXAMPLE 8 Polymerization of 4-(N-maleimido)phenylcyclobutenyl Ketone

Into a tube is placed 146 mg of4-(N-maleimido)-phenyl-4-benzocyclobutenyl ketone and nitrogen. The tubeis placed into a Wood's Metal bath at 150° C. The temperature iscontrolled and monitored with a heater and a thermocouple. The followingsequence of times and temperatures are applied to the tube:

    ______________________________________                                        150° C.       30 min.                                                  180° C.       30 min.                                                  210° C.       30 min.                                                  235° C.       1 hour                                                   260° C.       1 hour                                                   270° C.       1 hour                                                   ______________________________________                                    

At the end of the sequence, the heating is stopped and the tube andthermocouple are removed from the heating bath. The tube is allowed tocool overnight. The polymer is an amber color with small voids trappedin the matrix. The polymer is physically broken into small pieces. A TGAis run on one of the pieces, 0.05 wt % loss occurs at 327.78° C. and 5%weight loss at 464.39° C.

What is claimed is:
 1. A polymeric composition which comprises a polymerof one or more compounds which correspond to the formula ##STR51##wherein Ar is an aromatic radical:R¹ is separately in each occurrence ahydrocarbyl, hydrocarbyloxy, hydrocarbylthio, an electron-donating orelectron-withdrawing group; R² is separately in each occurrencehydrogen, cyano, halo or an electron donating group; R³ is separately ineach occurrence hydrogen, a hydrocarbyl, hydrocarbyloxy orhydrocarbylthio group; Y is a direct bond or a divalent organic radical;and a is an integer of from 0 to 3; with the proviso that the two carbonatoms of the (C(R²)₂)₂ moiety which are bound to Ar are bound toadjacent carbon atoms on the same aromatic ring of Ar; with the furtherproviso that the moieties R¹, R² and R³ do not interfere with thepolymerization of the compound.
 2. The polymeric composition of claim 1which contains units corresponding to the formula ##STR52## wherein Aris an aromatic radical;R¹ is separately in each occurrence ahydrocarbyl, hydrocarbyloxy, hydrocarbylthio, an electron-donating orelectron-withdrawing group; R² is separately in each occurrencehydrogen, cyano, halo or an electron donating group; R³ is separately ineach occurrence hydrogen, a hydrocarbyl, hydrocarbyloxy orhydrocarbylthio group; Y is a direct bond or a divalent organic radical;and a is an integer of from 0 to 3; with the proviso that the C atoms ofthe C(R²)₂ moieties which are bound to Ar are bound to adjacent carbonatoms on the same aromatic ring of Ar; with the further proviso that themoieties R¹, R² and R³ do not interfere with the polymerization of thecompound.
 3. The polymeric composition of claim 2 which corresponds tothe formula ##STR53## wherein Ar is an aromatic radical;R¹ is separatelyin each occurrence a hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, anelectron-donating or electron-withdrawing group; R² is separately ineach occurrence hydrogen, cyano, halo or an electron donating group; R³is separately in each occurrence hydrogen, a hydrocarbyl, hydrocarbyloxyor hydrocarbylthio group; Y is a direct bond or a divalent organicradical; and a is an integer of from 0 to 3; and c is a real number of 2or greater; with the proviso that the C atoms of the C(R²)₂ moietieswhich are bound to Ar are bound to adjacent carbon atoms on the samearomatic ring of Ar; with the further proviso that the moieties R¹, R²and R³ do not interfere with the polymerization of the compound.
 4. Apolymeric composition which comprises the polymer of one or morecompounds which correspond to the formula ##STR54## wherein R¹ isseparately in each occurrence a hydrocarbyl, hydrocarbyloxy,hydrocarbylthio, an electron-donating or electron-withdrawing group;R²is separately in each occurrence hydrogen, cyano, halo or an electrondonating group; R³ is separately in each occurrence hydrogen, ahydrocarbyl, hydrocarbyloxy or hydrocarbylthio group; Y is a direct bondor a divalent organic radical; and b is an integer of from 0 to 3,inclusive; with the proviso that the moieties R¹, R² and R³ do notinterfere with the polymerization of the compound.
 5. The polymericcomposition of claim 4 which contains units which correspond to theformula ##STR55## wherein R¹ is separately in each occurrence ahydrocarbyl, hydrocarbyloxy, hydrocarbylthio, an electron-donating orelectron-withdrawing group;R² is separately in each occurrence hydrogen,cyano, halo or an electron donating group; R³ is separately in eachoccurrence hydrogen, a hydrocarbyl, hydrocarbyloxy or hydrocarbylthiogroup; Y is a direct bond or a divalent organic radical; and b is aninteger of from 0 to 3, inclusive; with the proviso that the moietiesR¹, R² and R³ do not interfere with the polymerization of the compound.6. The polymeric composition of claim 5 which corresponds to the formula##STR56## wherein R¹ is separately in each occurrence a hydrocarbyl,hydrocarbylthio, hydrocarbyloxy, electron-withdrawing orelectron-donating group;R² is separately in each occurrence hydrogen,cyano, halo or an electron donating group; R³ is separately in eachoccurrence hydrogen, a hydrocarbyl, hydrocarbyloxy or hydrocarbylthiogroup; Y is a direct bond or a divalent organic radical; b is an integerof from 0 to 3, inclusive; and d is an integer of 2 or greater with theproviso that the moieties R¹, R² and R³ do not interfere with theformation of the polymer.
 7. A polymeric composition which comprises theproduct prepared by exposing one or more compounds which correspond tothe formula ##STR57## wherein Ar is an aromatic radical;R¹ is separatelyin each occurrence a hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, anelectron-donating or electron-withdrawing group; R² is separately ineach occurrence hydrogen, cyano, halo or an electron-donating group; R³is separately in each occurrence hydrogen, a hydrocarbyl, hydrocarbyloxyor hydrocarbylthio group; Y is a direct bond or a divalent organicradical; and a is an integer of from 0 to 3; with the proviso that thetwo carbon atoms of the (C(R²)₂)₂ moiety which are bound to Ar are boundto adjacent carbon atoms on the same aromatic ring of Ar; with thefurther proviso that the moieties R¹, R² and R³ do not interfere withthe polymerization of the compound, to a temperature at which thecompound undergoes polymerization.
 8. The polymeric composition of claim7 wherein the polymerization temperature is 175° C. or greater.
 9. Thepolymeric composition of claim 8 wherein the polymerization temperatureis 200° C. or greater.